Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds

Wang, Tao; Zhang, Yirui; Huang, Botao; Cai, Bin; Rao, Reshma R.; Giordano, Livia; Sun, Shi‐Gang; Shao‐Horn, Yang

doi:10.1038/s41929-021-00668-0

Cited by 188 publications

(134 citation statements)

References 92 publications

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“…However, there is almost no stretching vibration signal for *OOH at ≈1150 cm −1 (Figure S23b, Supporting Information). [30,31] This fully confirms that there is almost no *OOH during ORR at 0.965-0.165 V. The above data indicate that there are almost no *OOH intermediates during ORR on (Zn, Cu)-NC. Instead, numerous *OH intermediates appeared on (Zn, Cu)-NC surface.…”

Section: Dft Calculationssupporting

confidence: 72%

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Deng

Qian

Liu

et al. 2022

Adv Funct Materials

136

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Dual–single‐atom catalysts with synergistic effect of adjacent atomic metal sites show a great potential for oxygen reduction reaction (ORR). Herein, a dynamical synthetic strategy is demonstrated for the rational design of dual‐atom catalyst ((Zn, Cu)−NC) with non‐covalent Cu and Zn sites as nitrogen‐doped carbon as support. Owing to the non‐covalent interaction of Zn and Cu atomic pair sites, (Zn, Cu)−NC exhibits significant performances for ORR, surpassing the catalysts with individual Zn or Cu site. The theoretical calculations reveal that (Zn, Cu)−NC can highly activate the linear O2 molecule via the non‐covalent interaction between Zn and Cu pairs, providing the more effective overlap between the metal 3d orbitals and O 2p orbital. Therefore, the ORR activity is optimized with the improvement of the adsorption configuration and adsorption energy of O2. Further, both liquid and quasi‐solid zinc−air batteries with (Zn, Cu)−NC as air cathodes achieve remarkable energy density and stability. This research proposes a facile synthetic strategy to construct single‐atom catalysts and presents an insightful understanding of the non‐covalent interplay between heteronuclear metal atoms in dual‐atom catalysts.

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Section: Dft Calculationssupporting

confidence: 72%

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Deng

Qian

Liu

et al. 2022

Adv Funct Materials

136

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“…Controllably tuning the catalytic activity of identified active sites based on adequately understood mechanisms is desired but challenging for the development of precious-metal-free electrocatalysts toward the oxygen reduction reaction (ORR). [1][2][3] Among the already recognized reactive moieties in the nonprecious metal-based ORR electrocatalysts, the metal-nitrogen (M-N x ) based moieties, especially the Fe-N 4 -based moieties, have been reported to possess the highest catalytic activity. [4][5][6][7] Fe-N 4 -based polymer with similar active sites and ORR activity as FePc.…”

Section: Introductionmentioning

confidence: 99%

Insight into the Mechanism of Axial Ligands Regulating the Catalytic Activity of Fe–N₄ Sites for Oxygen Reduction Reaction

Zhao

Liu

et al. 2022

Advanced Energy Materials

186

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Although the planar square Fe-N 4 is considered to be the basic unit of the active Fe-N 4 -based moieties, the exact local structure of such moieties has not yet been determined due to that the axial ligands and the second coordination sphere (i.e., the surrounding carbon matrix) of Fe-N 4 are unclear. [8] Based on the computational hydrogen electrode (CHE) model, the theoretical ORR onset potentials of Fe-N 4 in different models were as low as 0.25-0.43 V versus RHE (V RHE ), [9,10] much lower than the experimentally measured ones on Fe-N-C (0.82-0.95 V RHE ). Besides, some new active moieties in Fe-N-C (e.g., FeON 4 , Fe(OH)N 4 , and FeN 4 Cl) were proposed by using in situ characterizations or CHE modeling, [11][12][13][14] revealing that the axialligand coordination played a critical role in high-activity Fe-N 4 -based moieties. However, these studies were carried out on Fe-N-C that contained not only the Fe-N 4 sites but also a large number of other ORR active sites (such as the N-doped carbon and intrinsic defects of carbon), in which the implemented modifications would affect the ORR activities of different active sites and sometimes even alter the structure of the carbon matrix. [15] That is, the observed ORR activity improvement of the Fe-N-C after such modifications could not be solely attributed to the enhancement of the intrinsic ORR activity of Fe-N 4 and thus the mechanism associated with the improvement is still ambiguous. To this end, developing a model catalyst as a studying platform is highly demanded to reveal the regulation mechanism of axial-ligand coordination on the catalytic activity of Fe-N 4 sites.Iron porphyrin (FePr) and iron phthalocyanine (FePc) are widely used molecular model catalysts with Fe-N 4 as the only kind of ORR active sites. [16] Although some modified FePc and FePr with axially coordinated Fe-N 4 moieties have been reported in recent papers, [17][18][19] only a few strong ligands (e.g., CN − and pyridine) could perform such axial coordination due to that the FePc and FePr are more inclined to exist as the D4h symmetry structure with highly concentrated local electrons. [17] In order to systematically study the correlation between the axial ligands and the catalytic activity of Fe-N 4 sites, it is necessary to explore a Fe-N 4 -based molecular model catalyst with a stronger axial coordination ability. Poly(phthalocyanine iron) (PFePc) is an alkali-soluble Identifying the actual structure and tuning the catalytic activity of Fe-N 4based moieties, well-recognized high-activity sites in the oxygen reduction reaction (ORR) are challenging problems. Herein, by using poly(iron phthalocyanine) (PFePc) as an Fe-N 4 -based model electrocatalyst, a mechanistic insight into the effect of axial ligands on the ORR catalytic activity of Fe-N 4 is provided and it is revealed that the ORR activity of Fe-N 4 sites with OH desorption as a rate-determining step is related to the energy level gap between the OH p x p y and Fe 3d z 2 , which can be tuned by regulating the field strength of the...

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“…S52). Which consistent with proton-coupled electron transfer (PCET) instead of hydrogen atom transfer (HAT) decreasing the transfer barrier because electrons and protons were transferred to one receptor and pH dependent to accumulate the charge [24][25][26][27] . Under alkaline and neutral conditions, the ORR was accompanied by increased pH, causing an insu cient proton supply 6 .…”

Section: Mechanism Of Modulated Electrolytesmentioning

confidence: 73%

“…Under alkaline and neutral conditions, the ORR was accompanied by increased pH, causing an insu cient proton supply 6 . Finite element analysis also veri ed that H 2 O 2 had a wider distribution in acidic electrolytes 24 than in alkaline and neutral electrolytes (Figs. 3e-g).…”

Section: Mechanism Of Modulated Electrolytesmentioning

confidence: 84%

Enduring and Instant H2O2 Generation via Controlled Coupling Transfer

Zhao¹,

Duan

et al. 2022

Preprint

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Extremely slow kinetics and limited accumulation of H2O2 during the oxygen reduction reaction, which derives from the negative effects of diffusion-limited and further catalysis, are the grant challenges seriously hindering the development of green H2O2 synthesis. Herein, we first controlled the coupling energy of the proton and electron by periodic-potential-driven catalysis, achieving 56-fold greater H2O2 accumulation than that generated by constant-potential catalysis. To modulate proton and electron coupling transfer, we employed optimized dual-electrolytes to achieve a rate of 45900 mmol gcat−1 h− 1, and provided strong evidence of molecular-level understanding via comprehensive microenvironment simulation. These results were obtained with a pyrolytic metal/reduced cage crystal (RCC1) catalyst with stable performance reaching 3.6 million pulses, which generated products that can be directly utilized for the complete removal of bacteria in 2 seconds from seawater. Our systemic methodology and in situ application are anticipated to aid in the design of innovative catalysts, provide a deep understanding of pulse and electrolyte effects, and aid in the design of a new effective cell system to achieve industry-level H2O2 production.

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Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds

Cited by 188 publications

References 92 publications

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Insight into the Mechanism of Axial Ligands Regulating the Catalytic Activity of Fe–N₄ Sites for Oxygen Reduction Reaction

Enduring and Instant H2O2 Generation via Controlled Coupling Transfer

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Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds

Cited by 188 publications

References 92 publications

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Non‐Covalent Interaction of Atomically Dispersed Cu and Zn Pair Sites for Efficient Oxygen Reduction Reaction

Insight into the Mechanism of Axial Ligands Regulating the Catalytic Activity of Fe–N4 Sites for Oxygen Reduction Reaction

Enduring and Instant H2O2 Generation via Controlled Coupling Transfer

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Insight into the Mechanism of Axial Ligands Regulating the Catalytic Activity of Fe–N₄ Sites for Oxygen Reduction Reaction